Nonyl alcohols with a low degree of branching and their derivatives

ABSTRACT

The invention relates to nonyl alcohols with a low degree of branching and derivatives produced using them. In particular the present invention relates to mixture of primary nonyl alcohols in which at least 80% of the alkyl chains are linear and at least 15% of the alkyl chains are branched at the 2-carbon position and its derivatives. The low degree of branching produces derivatives that are more elongated and less bulky that similar derivatives produced with more highly branched alcohols.

PRIORITY CLAIM

The present application claims the benefit to priority of U.S.Provisional Application No. 61/492,067 entitled “Nonyl Alcohols with aLow Degree of Branching and Their Derivatives” filed Jun. 1, 2011.

FIELD OF THE INVENTION

The invention relates to nonyl alcohols with a low degree of branchingand derivatives produced using them.

BACKGROUND OF THE INVENTION

Nonyl alcohols are well known and commonly used to synthesizeplasticizers and surface active agents. The most common nonyl alcohol isa totally branched nonyl alcohol known as isononyl alcohol. Isononylalcohol is most commonly produced by dimerizing butene and performingthe oxo hydroformylation reaction as described in Industrial OrganicChemicals; Wittcoff, Harold A., Reuben, Bryan G., and Plotkin, JeffreyS., Wiley-Interscience, 2004. This alcohol is sold commercially byExxonMobil Corporation under the trade name Exxal® 9. A second type ofnonyl alcohol is produced by performing the oxo hydroformylationreaction on a linear octene. This yields a nonyl alcohol containingbetween 35 and 65% branched species.

While both types of nonyl alcohol can be used to synthesize usefulderivatives like plasticizers and surface active agents, the high degreeof branching limits the functionality of these derivatives. There is aneed for a nonyl alcohol that can be produced with a lower proportion ofbranched species.

SUMMARY OF THE INVENTION

The present invention provides a nonyl alcohol with a low degree ofbranching and derivatives made therefrom. The more elongated and lessbulky molecular character of this nonyl alcohol confers superiorcharacteristics to derivatives derived from it. This is particularlyapparent in plasticizer and surface active agent derivatives.Plasticizer derivatives made with this nonyl alcohol exhibit lessvolatility, more resistance to environmental damage, and superiorresponse to temperature extremes in use, when compared to similarplasticizers produced with more highly branched nonyl alcohols. Surfaceactive agents made with this nonyl alcohol exhibit better detergency andsoil adsorption than similar surface active agents made with more highlybranched nonyl alcohols. In addition they are more readily biodegradedin the environment.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is a mixture of primary nonyl alcohols in which atleast 80% of the alkyl chains are linear and at least 15% of the alkylchains are branched at the 2-carbon position as well as derivatives ofthis alcohol. The derivatives include esters of dicarboxylic acids orother polyacids useful as plasticizers as well as alkoxylated alcohols,sulfated alcohols, sulfated alkoxylated alcohols, alcohol ether amines,or other derivatives with hydrophilic moieties useful as surface activeagents.

The linear nonyl alcohols have the structure:

H—CH₂—CH₂—CH₂—CH₂—CH₂—CH₂—CH₂—CH₂—CH₂—OH  (1)

The branched nonyl alcohols have the general structure:

where R₁ and R₂ are linear alkyl chains containing a total of 7 carbonatoms between them.

Mixtures having the composition of approximately 82% of structure (1)and 18% of structure (2) can be synthesized from linear octene by themodified Oxo process, using a phosphine, phosphite, arsine, or pyridineligand modified cobalt or rhodium catalyst, as described in U.S. Pat.Nos. 3,231,621; 3,239,566; 3,239,569; 3,239,570; 3,239,571; 3,420,898;3,440,291; 3,448,158; 3,448,157; 3,496,203; 3,496,204; 3,501,515;3,527,818, the disclosures of which are incorporated herein byreference.

Hydroformylation is a term used in the art to denote the reaction of anolefin with CO and H₂ to produce an aldehyde/alcohol which has one morecarbon atom than the reactant olefin. Frequently in the art the termhydroformylation is utilized to cover the aldehyde and the reduction tothe alcohol step in total, i.e., hydroformylation refers to theproduction of alcohols from olefins via carbonylation and an aldehydereduction process. As used herein, hydroformylation refers to theultimate production of alcohols.

Alcohol derivatives useful as plasticizers are well known in the art.Synthesis and properties of common plasticizers are disclosed inTechnology of Plasticizers; Sears, J. Kern and Darby, Joseph R., JohnWiley & Sons, 1982 and references cited therein. The present inventionincludes plasticizers synthesized from a mixture of primary nonylalcohols in which at least 80% of the alkyl chains are linear and atleast 15% of the alkyl chains are branched at the 2-carbon position. Apreferred embodiment of this invention comprises diesters of the novelnonyl alcohol mixture with diacids. Common diacids that can beesterified to produce plasticizers include phthalic acid, adipic acid,sebacic acid, and succinic acid. An additional preferred embodiment ofthis invention includes polyesters of polyacids containing three or moreacid moieties. Common polyacids that can be esterified to produceplasticizers include trimellitic acid and terephthalic acid.

Alcohol derivatives useful as surface active agents are well known inthe art. Synthesis and properties of common surface active agents aredisclosed in Handbook of Detergents Part F: Production, Zoller, Uri andSosis, Paul CRC Press, 2009 and references cited therein.

The present invention includes surface active agents synthesized from amixture of primary nonyl alcohols in which at least 80% of the alkylchains are linear and at least 15% of the alkyl chains are branched atthe 2-carbon position. Preferred embodiments of this invention includepolyalkoxylates, sulfates, sulfated polyalkoxylates, and ether amines ofthe novel nonyl alcohol mixture.

Example 1

In an air-free environment, 1.5 kg of octene was combined with 67 g ofphosphine modified cobalt catalyst and stirred overnight to dissolve. A1 gallon autoclave was purged with nitrogen and the solution added. Thereactor was pressurized with 2/1 ratio of H₂/CO to 6.89 MPa and heatedto 200° C. with stirring for 7 hours. The hydroformylated reactionproduct was vacuum distilled to recover 998 g of the hydroformylatedoctene.

While stirring and under a constantly flowing dry nitrogen atmosphere,this crude hydroformylated octene was treated with 6.25 g of sodiumborohydride to saponify any esters and reduce any aldehydes formed inthe hydroformylation reaction. The temperature was raised to 50° C. andheld for 3 hours while stirring continued. At the end of 3 hours anadditional 6.25 g of sodium borohydride was added. The temperature wasraised to 90° C. and held for 3.5 hours under constant stirring. Themixture was allowed to cool and stirring stopped while a dry nitrogenatmosphere was maintained.

The resultant crude alcohol mixture was heated to 80° C., whilemaintaining constant stirring and a flow of dry nitrogen. Then 100 ml ofwarm (90° C.) deionized water was added slowly to the crude alcoholmixture. After the first 100 ml of deionized water was added, anadditional 400 ml of warm water was added at a slow rate. Stirring wasmaintained for 30 minutes. Heating and stirring were discontinued andthe crude alcohol/water mixture was allowed to separate into 2 phases.The water phase was then removed.

This water-washing step was repeated two additional times. The crudealcohol was then vacuum distilled to separate the mixture of nonylalcohols from light and heavy by-products. The total yield of mixednonyl alcohols was 918 g. Approximately 82% of the alkyl chains werelinear and 18% were branched at the 2-carbon position.

Example 2

567 g of nonyl alcohol produced in Example 1 was combined with 280 g ofphthalic anhydride, 200 g of toluene and 5.5 g of methanesulfonic acid.The reaction was set up for reflux through a Dean-Stark trap using anitrogen purge and slow stirring. The reactor contents were refluxed for5 hours. Residual catalyst was neutralized with a 10% NaCO₃ solution andthe product was water washed. The product was purified by vacuumstripping and distillation to yield 818 g of dinonyl phthalate.

Example 3

567 g of branched isononyl alcohol (Exxal®9, ExxonMobil Corporation) wastreated according to the procedure of Example 2. The reaction yielded809 g of isononyl phthalate.

Plasticizer Performance

Samples of plasticized PVC were prepared with the plasticizers ofExamples 2 and 3. In each case 67 parts of the plasticizer was combinedwith 100 parts of the PVC resin.

A control sample was also prepared using the plasticizerdi(ethylhexyl)phthalate. Several critical physical properties weremeasured for each sample. In each case the measurement was scaled to theresult for the sample plasticized with di(ethylhexyl)phthalate. Resultsare shown in the tables 1, 2 and 3 below.

TABLE 1 Property Volatility (% plasticizer lost in 24 hour at 87° C.)Plasticizer Di(ethylhexyl)phthalate Diisononyl phthalate Dinonylphthalate Result 100 60 43

TABLE 2 Property Efficiency (Reciprocal of Shore “A” Hardness)Plasticizer Di(ethylhexyl)phthalate Diisononyl phthalate Dinonylphthalate Result 100 93 98

TABLE 3 Property Low temperature flexibility (T_(f) ° C.) Plasticizer:Di(ethylhexyl)phthalate Diisononyl phthalate Dinonyl phthalate Result:100 108 123

The volatility result shows that the dinonyl phthalate plasticizer ismuch more resistant to evaporation than is the diisononyl phthalate. Theefficiency result shows that dinonyl phthalate will plasticize PVC to agreater extent than diisononyl phthalate at equal loading. The lowtemperature flexibility result shows that PVC plasticized with dinonylphthalate retains flexibility at lower temperature than PVC plasticizedwith diisononyl phthalate. These three results combine to illustrate thebenefits seen when this novel mixed nonyl alcohol is used to producephthalate derivatives. Similar benefits are expected for other classesof plasticizers as well.

Example 4

300 g of nonyl alcohol from Example 1 was purged with dry nitrogen gasfor 30 minutes in a flask fitted with a Dean-Stark trap. 1.01 g of KOHwas added and the flask was heated to 120° C. for 90 minutes. Thecontents were transferred to an autoclave and pressurized to 137.9 kPawith nitrogen. The autoclave was heated to 165° C. and 275 g of ethyleneoxide was slowly added. The autoclave was maintained at temperature for2 hours, then cooled and emptied. The excess catalyst was neutralizedwith 0.92 g of acetic acid. 572 g of nonyl(EO)₃ were recovered.

Example 5

The procedure of Example 4 was repeated using 1.82 g of KOH, 733 g ofethylene oxide and 1.65 g of acetic acid. 1025 g of nonyl(EO)₈ wererecovered

Example 6

The procedure of Example 4 was repeated using 300 g of branched isononylalcohol (Exxal®9, ExxonMobil Corporation). 571 g of isononyl(EO)₃ wererecovered.

Example 7

The procedure of Example 4 was repeated using 300 g of branched isononylalcohol (Exxal®9, ExxonMobil Corporation), 1.82 g of KOH, 733 g ofethylene oxide and 1.65 g of acetic acid. 1026 g of isononyl(EO)₈ wererecovered

Surface Active Agents 1. Hard Surface Cleaning Application

The products described in Examples 4-7 were used to create two simpleformulations to demonstrate the practical benefits of using surfaceactive agents derived from this novel nonyl alcohol mixture to cleanhard surfaces. The composition of the formulations is shown in Table 4.

TABLE 4 Formula 1 Formula 2 Nonyl(EO)₃ 2.0% Nonyl(EO)₈ 2.0%Isononyl(EO)₃ 2.0% Isononyl(EO)₈ 2.0% Sodium Carbonate 0.5% 0.5% Water95.5% 95.5%

White vinyl tiles were stained with a standard oily soil prepared inaccordance with ASTM D 4828-92. Reflectance measurements on the soiledtiles were conducted. Each tile was sprayed with 5 ml of either Formula1 or Formula 2 and was wiped three times with a damp sponge. Reflectancemeasurements of the cleaned areas of the tile were taken. Soil removalwas calculated as the difference between the two reflectancemeasurements divided by the reflectance measurement of the soiled tile.Each formula was tested on 10 tiles and the soil removal numbers wereaveraged and are shown in Table 5.

TABLE 5 Soil Removal Formula 1 92% Formula 2 67%

2. Laundry Cleaning Application

The products described in Examples 5 and 7 were used to create twosimple formulations to demonstrate the practical benefits of usingsurface active agents derived from this novel nonyl alcohol mixture in alaundry cleaning application. The composition of the formulations isshown in Table 6.

TABLE 6 Formula 3 Formula 4 (C₁₂-C₁₅)(EO)₃SO₃ 10.0% 10.0% Nonyl(EO)₈5.0% Isononyl(EO)₈ 5.0% Sodium Citrate 5.0% 5.0% Triethanolamine 5.0%5.0% Water 75.0% 75.0%

In this demonstration, 9 test cloths of either 100% cotton or apolyester/cotton blend were soiled with a mixture of dust and syntheticsebum. Each was individually marked and an optical brightnessmeasurement of each was made.

An aqueous solution of the following composition was prepared:

2.0 g/l Formula 3 150 ppm Ca/Mg water hardness

The test cloths were washed in this solution in a controlled manner at20° C., rinsed, and dried. Optical brightness measurements were repeatedand the proportion of soil removed from each was calculated from theoptical brightness measurements. Soil removal for the 9 test cloths wasaveraged and the average is reported in the table below.

Another demonstration was performed in the same manner using a solutionof the following composition:

2.0 g/l Formula 4 150 ppm Ca/Mg water hardness

Soil removal results are reported in Table 7.

TABLE 7 Formula 3 solution Formula 4 solution Soil removal from 100%35.3% 25.2% cotton test cloths Soil removal from 65.3% 47.5%polyester/cotton test cloths

These results show that the detergency of the Formula 3 solution issubstantially better than the detergency of the Formula 4 solution,indicating that the surfactant in Example 5 can provide superiorcleaning benefits to the surfactant in Example 7 when used in a typicallaundry detergent formulation.

This demonstrates the advantage of the novel mixed nonyl alcohol whenderivatized to a typical class of surface active agents. Similaradvantages are expected when it is derivatized to other classes ofsurface active agents as well.

1. A mixture of nonyl alcohols comprising at least 80% linear nonylalcohols and at least 15% of branched nonyl alcohols having branching atthe 2-carbon position.
 2. A mixture of derivatives of nonyl alcoholsproduced by derivatizing a mixture of nonyl alcohols comprising at least80% linear nonyl alcohols and at least 15% of branched nonyl alcoholshaving branching at the 2-carbon position.
 3. A mixture as claimed inclaim 2 wherein the derivatives comprise esters of dicarboxylic acids,esters of polycarboxylic acids, alkoxylated alcohols, sulfated alcohols,sulfated alkoxylated alcohols, and alcohol ether amines.
 4. Aplasticizer comprising a diester of a mixture of nonyl alcoholscomprising at least 80% linear nonyl alcohols and at least 15% ofbranched nonyl alcohols having branching at the 2-carbon position withone or more diacids.
 5. A plasticizer as claimed in claim 4 wherein thediacid comprises phthalic acid, adipic acid, sebacic acid and succinicacid.
 6. A plasticizer comprising a polyester of a mixture of nonylalcohols comprising at least 80% linear nonyl alcohols and at least 15%of branched nonyl alcohols having branching at the 2-carbon positionwith one or more polyacids.
 7. A plasticizer as claimed in claim 6wherein the polyacid comprises trimellitic acid and terephthalic acid.8. An alcohol derivative comprising a polyalkoxylate, sulfate, sulfatedpolyalkoxylate, or ether amine of a mixture of nonyl alcohols comprisingat least 80% linear nonyl alcohols and at least 15% of branched nonylalcohols having branching at the 2-carbon position.
 9. A hard surfacecleaning formulation containing an alcohol derivative as claimed inclaim
 8. 10. A laundry detergent formulation containing an alcoholderivative as claimed in claim 8.